Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
  • C07D319/22—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one naphthalene or hydrogenated naphthalene ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
  • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
  • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D319/20—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring with substituents attached to the hetero ring

Definitions

• the present invention relates to a process for the preparation of 2,2,3,3-tetrafluoro-1,4-benzodioxanes, new intermediates that occur in this process and process for their manufacture.
• 2,2,3,3-tetrafluoro-1,4-benzodioxane are used as intermediates needed in the manufacture of active ingredients for pharmacy and agriculture (see e.g. DE-A 37 16 652, DE-A 19 501 367, DE-A 4 415 435 and DE-A 4 217 725).
• the compounds of formula (IV) are partly commercially available or according to known Methods or similarly producible. 1,2-dibromo-1,1,2,2-tetrafluoroethane is as Extinguishing media commercially available.
• the compounds which can be prepared according to the invention are represented by the formulas (I), (II) and (III) defines the compounds of the invention by the formulas (II) and (III), wherein however, in formula (II) the compound 1- (2-bromo-1,1,2,2-tetrafluoroethoxy) -2-methoxy-4 nitro-benzene is excluded.
• Preferred, particularly preferred and very particularly preferred compounds of Formulas (I), (II), (III) and (IV) are those in which a combination of the above designated meanings is present.
• Hydrocarbon residues such as alkyl can each be straight chain or branched.
• Optionally substituted radicals can be single or multiple, e.g. up to triple, be substituted, the substituents being identical or different in the case of multiple substitutions could be.
• alkali metal and alkaline earth metal hydrides such as sodium hydride, Sodium, potassium and ammonium hydroxide, sodium amide, lithium diisopropylamide, sodium methylate, Sodium ethylate, potassium tert-butoxide, sodium, potassium, calcium and Ammonium acetate, sodium, potassium and ammonium carbonate, sodium and potassium hydrogen carbonate, and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaimino
• This reaction is preferably carried out in the presence of a diluent.
• a diluent e.g. dipolar aprotic solvents and mixtures thereof.
• dipolar aprotic solvents examples include: nitriles such as acetonitrile, propionitrile, n- and i-butyronitrile and Benzonitrile, amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone and hexamethylphosphoric triamide, N-oxides such as N-methylmorpholine-N-oxide, esters such as methyl, ethyl or butyl acetate, sulfoxides such as dimethyl sulfoxide and sulfones such as sulfolane. Dimethyl sulfoxide is preferred.
• the temperature can be varied within a wide range in this reaction. in the generally one works at 20 to 130 ° C, preferably at 70 to 120 ° C.
• This reaction can be carried out under normal pressure or elevated pressure. It is advantageous to work in a closed vessel, which then during the Reaction can set a pressure of up to 10 bar, for example.
• reaction, workup and isolation of the reaction products can done according to generally accepted procedures.
• the compounds of the formulas (III) and (V) can, if desired, for example by distillation or column chromatography be separated.
• the compounds of the formulas (III) and (V) are preferably however, not separately, but their mixture is further implemented.
• ether cleavage of compounds of formula (III) to phenols of formula (II) can be carried out according to methods known per se.
• aqueous hydrohalic acids such as hydrogen iodide, hydrogen bromide or hydrogen chloride are used and, if appropriate, the process is carried out in the presence of a C 1 -C 4 -carboxylic acid such as formic or acetic acid as a solubilizer.
• concentration of the hydrohalic acid is preferably between 20% by weight and the saturation concentration. You can also use gaseous hydrohalic acid and then preferably work in an autoclave.
• the ether cleavage is preferably carried out by catalytic hydrogenation.
• suitable catalysts are Raney nickel or palladium-on-carbon, and solvents such as methanol, ethanol or ethyl acetate are suitable.
• the target product of the synthesis sequence is a benzodioxane of the formula (I) in which at least one of the radicals R 1 to R 4 is -C (OR 7 ) 2 R 6 , it is therefore advantageous to start from a corresponding single benzyl-protected catechol of the formula (IV) in which R 5 is benzyl, and to carry out the ether cleavage as a catalytic hydrogenation.
• the ketal or acetal function can also be produced again or for the first time at the end of the synthesis from the carbonyl function -CO-R 6 .
• the temperature in ether cleavage can be varied within a wide range. For example, with acidic cleavage at 30 to 150 ° C, preferably 50 to Work at 140 ° C. In catalytic hydrogenation, for example, at 0 to 50 ° C, preferably work at room temperature.
• the amount of acid to be used is not upwards critical. It is expedient to use per mole of the compound of the formula (III) at least the theoretically required amount of 1 mol of hydrohalic acid. Reactants and auxiliaries are preferably used in such amounts that during the acidic ether cleavage give a largely homogeneous solution.
• aqueous hydrobromic acid at a concentration of 30 to 70 is used % By weight and acetic acid in a concentration of 80 to 100% by weight in the weight ratio 1: 1.5 to 1: 3, initially dissolves the compound of formula (III) in of the acetic acid and then adds the hydrobromic acid.
• reaction, workup and isolation of the reaction products can done according to usual procedures.
• Compounds of the formulas (II) and (VI) can if desired, separated for example by distillation or column chromatography become.
• the compounds of the formulas (II) and (VI) are preferably not separated, but their mixture further implemented.
• the cyclocondensation of the phenols of the formula (II) to the benzodioxanes of the formula (I) is carried out in the presence of an acid binder.
• an acid binder e.g. those in question above for the implementation of compounds of formula (IV) to give compounds of formula (III).
• Phenols of the formula (II) to the benzodioxanes of the formula (I) are acid binders Sodium hydroxide, potassium hydroxide, sodium methylate and potassium methylate are preferred.
• This cyclocondensation can optionally be in the presence of a diluent be performed.
• Suitable diluents are e.g. higher boiling dipolar aprotic Solvents such as sulfones, especially sulfolane. A diluent is preferred used.
• This cyclocondensation can e.g. at 80 to 180 ° C, preferably at 100 to Carry out at 140 ° C.
• reaction, workup and isolation of the reaction products can done according to generally accepted procedures.
• All process steps can be carried out continuously or discontinuously, especially the cyclization.
• the method according to the invention also permits Manufacture of substituted 2,2,3,3-tetrafluoro-1,4-benzodioxane directly in good yields. It can also be carried out and avoided in a technically simple manner corrosive media such as chlorine and hydrogen fluoride.
• the percentage compositions of products and starting materials determined by GC relate to the area ratios (area%) of the signals of a flame ionization detector and are therefore generally not identical to Mol- or Weight percent.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

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• 1997
  • 1997-07-24 DE DE19731785A patent/DE19731785A1/de not_active Withdrawn
• 1998
  • 1998-07-13 DE DE59813152T patent/DE59813152D1/de not_active Expired - Fee Related
  • 1998-07-13 EP EP98112967A patent/EP0893444B1/fr not_active Expired - Lifetime
  • 1998-07-13 ES ES98112967T patent/ES2251750T3/es not_active Expired - Lifetime
  • 1998-07-16 JP JP10218627A patent/JPH11106383A/ja not_active Withdrawn
  • 1998-07-23 US US09/121,400 patent/US5936102A/en not_active Expired - Fee Related

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